Polyesters containing aminoalkylphosphonates

ABSTRACT

Selected phosphorus compounds, carbonyl compounds and alkanolamines are reacted to produce compounds of the formula:   WHEREIN M AND N ARE ZERO TO TWO AND M + N EQUALS TWO; A IS ZERO TO 1, B IS 1 TO 2 AND A + B EQUALS 2; X is oxygen or sulfur; R1, R2, R3, and R4 are organic radicals and R3 and R4 can also be hydrogen, and R5 is an alkyl group. Such compounds can be reacted with carboxylic compounds to produce polyesters, or with epoxides to form polyethers. Such polyesters and polyethers, as well as the compounds themselves, can be reacted with isocyanates to produce polyurethane compositions. When the reaction is carried out in the presence of a foaming agent, cellular products are produced.

United States Patent Iliopulos et'al.

[54] POLYESTERS CONTAINING AMINOALKYLPHOSPHONATES [72] lnventors:Miltiadis 1. lliopulos, Vienna, W. Va.;

Raymond l-lindersinn, Lewiston, N .Y.

[7 3] Assignee: Borg-Wamer Corporation, Chicago, 111.

[22] Filed: Dec. 22, 1969 [21] Appl. No.: 887,361

Related [1.8. Application Data [62] Division of Ser. No. 714,370, Nov.9, 1967, abandoned, which is a division of Ser. No. 158,877, Dec.

12, 1961, Pat. No. 3,385,914.

' 51] lnt.Cl. ..C08g17/133,C08g22/10,C08g22/14 [58] Field of Search..260/75 P, 75

[56] References Cited UNITED STATES PATENTS 3,076,010 H1963 Beck et a1..260/461 1 July 4,1972

3,440,222 4/ 1969 Walsh et a1. ..260/75 Primary Examiner-William 11.Short Assistant ExaminerL. L. Lee

Attorney-William S, McCurry and Roger A. Schmiege [5 7] ABSTRACTSelected phosphorus compounds, carbonyl compounds and alkanolamines arereacted to produce compounds of the formula:

wherein m and n are zero to two and m n equals two; a is zero to l, b isl to 2 and a b equals 2; X is oxygen or sulfur; R,, R R and R, areorganic radicals and R and R can also be hydrogen, and R is an alkylgroup. Such compounds can be reacted with carboxylic compounds toproduce polyesters, or with epoxides to form polyethers. Such polyestersand polyethers, as well as the compounds themselves, can be reacted withisocyanates to produce polyurethane compositions. When the reaction iscarried out in the presence of a foaming agent, cellular products areproduced.

4 Claims, No Drawings POLYESTERS CONTAINING AMINOALKYLPHOSPHONATESREFERENCE TO PRIOR APPLICATIONS This is a division of copendingapplication Ser. No. 714,370, filed Nov. 9, 1967, now U.S. Pat. No.3,501,421, which is a division of copending application Ser. No.158,877, filed Dec. 12, 1961, now U.S. Pat. No. 3,385,914.

This invention relates to novel phosphorus-containing polyesters whichproducts are useful as binders, casting resins, laminating resins, andcoating compositions.

In accordance with this invention there are provided polyesters ofcomponents comprising a polycarboxylic compound and a polyhydricalcohol, having chemically combined therein a compound of the formula:

wherein m and n are zero to 2, and m+n equals 2; a is zero to l, b is 1to 2, and a+b equals 2; R, and R are alkyl, cycloalkyl, alkenyl, aryl,alkylaryl or halogen-substituted organic radicals of the foregoinggroup; R and R are hydrogen, alkyl, cycloalkyl, alkenyl, aryl,alkylaryl, arylalkyl or halogen-substituted radicals of the foregoinggroup, R is alkyl, and X is oxygen or sulfur. The preferred phosphoruscompounds of the invention have the formula:

Most preferred as the phosphorus compound is the compounddimethyl-N-(2'2-aminoisopropyl-2- phosphonate.

This invention relates to novel phosphorus-containing monomers that arecapable of being polymerized to useful products. In other aspects, theinvention relates to novel phosphorus-containing polymers such aspolyesters.

It is known that polymers can be rendered fire-resistant byincorporating phosphorus therein. However, it is most desirable tochemically combine the phosphorus into the polymer to prevent the lossof phosphorus by leaching or weathering of the polymer. In the past,phosphorus-containing polymers have been prepared as esters of variousphosphorus acids wherein the phosphorus ester linkages formed theback-bone of the polymers. This approach has not been completelysuccessful because of the tendency of the phosphorus ester to hydrolyzein the presence of water, which phenomenon results in the degradation ofthe polymer and the loss of its valuable physical properties. Hencethere is a need to overcome these difficulties, and yet produce usefulpolymers with inexpensive materials.

Accordingly, it is an object of this invention to produce polymers thatare both fire-resistant and have good hydrolytic stability. It isanother object of the invention to produce novel monomers that arecapable of polymerizing to produce such polymers. It is a further objectto produce novel polyesters that contain phosphorus which are useful inthe preparation of castings, laminates, and reinforced plastic articles.Still other objects and advantages of the present invention will be apparent to those skilled in the art upon consideration of the followingdetailed description.

These and other objects are satisfied by providing novel compositionshaving the following chemical structure:

wherein m and n have a numerical value of zero through 2 and m+n equals2; a has a value ofzero or 1, b has a value of 1 or 2, and a+b equals 2;X is oxygen or sulfur; R,, R R R are organic radicals selected from thegroup consisting of alkyl, cycloalkyl, alkenyl, aryl, alkylaryl,arylalkyl, and halo-substituted organic radicals of the foregoing group;and R, can also be hydrogen, and R is an alkyl group.

These hydroxyl-containing monomers can be reacted with carboxyliccompounds to produce polyesters. When the polyesters are unsaturatedthey can be cross-linked to form thermosetting polymers by reaction withethylenically unsaturated monomers and/or in the presence of freeradical catalysts.

The novel monomers of the invention are produced by reacting together anorganic compound, a carbonyl compound and a primary or secondary amine.The organic phosphites that can be used in the invention are thosehaving the chemical formula:

.. wherein m, n, R,, R and X are as defined hereinbefore. Among thepreferred phosphorus compounds for use in prac ticing the invention arelower alkyl phosphites such as dirnethyl phosphite and lower alkenylphosphites such as diallyl phosphite. Other specific phosphites that canbe used are those wherein the radicals R, and R are methyl, ethyl,isopropyl, butyl, hexyl, n-octyl, 2-ethyl-hexyl, decyl, hexadecyl,phenyl, benzyl, tolyl, cyclohexyl, allyl, crotonyl, betachloroethyl,beta-bromoethyl, and mixtures thereof.

In general, the length of the carbon chains or number of carbon atoms inthe aryl nuclei of the organic radicals of the phosphorus compounds isnot critical, and can vary over wide ranges. The lower limit is thelowest possible number of carbon atoms such as one carbon atom in thealkyl groups and six carbon atoms in the aryl groups, and the upperlimit is practical in nature. However, a higher percent by weight ofphosphorus may be incorporated in the polymer in instances where theorganic radicals attached to the phosphorus atoms are of minimum length,and thus the carbon atoms in the organic radicals R, and R preferablyshould contain from one to about six to eight carbon atoms.

The carbonyl compounds are preferably aldehydes and ketones. Thepreferred aldehydes are those containing not more than eight carbonatoms. Suitable compounds of this class are formaldehyde, acetaldehyde,propionaldehyde butyraldehydes, benzaldehydes, 2-ethylhexanal,ethylbutyraldehyde, heptaldehyde, and the like. The ketones that areuseful in the invention have the structural formula:

The organic radicals R and R are groups such as methyl, ethyl,isopropyl, butyl, hexyl, n-octyl, Z-ethylhexyl, phenyl, benzyl, tolyl,cyclohexyl, allyl, and mixtures thereof. It is generally preferred thatthe number of carbon atoms in each organic radical R and R. does notexceed eight.

The preferred amines are those having the structural formula:

wherein a has a value of zero or 1, b has a value of l or 2, and a+bequals 2, X is oxygen or sulfur and the organic radical R is an alkylgroup having not more than eight carbon atoms. Typical amines for use inpreparing the compounds of the in vention are ethanolamine,2-aminopropanol, 3- aminopropanol, 2-aminobutanol, 3-aminobutanol, 4-aminobutanol, di(2-propanol)amine, di( 3-propanol) amine,

di( 2-butanol )amine, di( 3-butanol )amine, tanol )amine, and the like.

In the preparation of the polyfunctional monomers of this invention, itis preferred to maintain the reaction temperature at a low level inorder to inhibit the polymerization of the monomer products. Generally,it is preferred that the reaction temperature be less than 80 C, andpreferably less than 50 C. The reaction can be carried out in thepresence of a solvent, if desired, the only requirement being that thesolvent is not reactive with respect to any of the reactants. Suitablesolvents are alcohols, such as methanol, isopropanol, butanol and thelike; ethers such as diethyl ether, and dioxane, and hydrocarbons suchas hexane, heptane, octane, benzene, and cyclohexane.

The following examples illustrate the preparation of the monomers of theinvention.

di( 4-bu- EXAMPLE 1 :1. Preparation of dimethyl-N-(2'-hydroxyethyl)-2-aminoisopropyl-2-phosphonate C1130 CH:

Twenty-two grams of dimethylhydrogenphosphite, 12.2 grams ofethanolamine and two hundred milliliters of methanol were mixed to yielda homogeneous solution. Anhydrous sodium sulfate (50.0 grams), was addedto the solution. A solution of l 1.6 grams of acetone in fiftymilliliters of absolute methanol was added dropwise over a period ofapproximately minutes to keep the temperature of the reaction mixtureunder 50 C. The hot mixture was stirred for about 2 hours at roomtemperature until the temperature of the reaction was 25 C. The dryingagent was filtered off and the solvent was evaporated.

The yield of crude material was eighty-nine to ninety-five percent. Theproduct was an almost odorless, colorless oil. Anal. Calcd. for C H HOP: P, 14.66 percent Found: P, 15.0 percent.

b. Preparation and Characterizations of the picrate ofdimethyl-N-(2-hydroxyethyl)-2-aminoisopropyl-2- phosphonate.

Formula:

To a solution of 1.83 grams ofdimethyl-N-(2-hydroxyethyl)-2-amino-isopropyl-2-phosphonate in 200milliliters of anhydrous ether was added with stirring a solution of3.07 grams of picric acid in four hundred milliliters of ether. Ayellowish precipitate formed.

The crude picrate is soluble in alcohols, slightly soluble in benzeneand hydrocarbons.

The crude picrate is recrystallized from hot chloroform by adding etherto the cloud point and the cooling the solution to minus twenty degreescentigrade. It can also be recrystallized from ethylacetate ethermixtures. The purified salt, crystallizing as yellow needles, sinters at127 C and melts at 128.5 to 129 C, (uncorrected) with decomposition.

spectroscopy) EXAMPLE 2 a. Preparation of dimethyl-N-(Z-hydroxyethy1)-2-0 arninoethyl-Z-phosphonate.

(jll fill Twenty-two grams of dimethylhydrogenphosphite, 12.2 grams ofethanolamine and 300 milliliters of absolute methanol were mixed toyield a homogeneous solution. Fifty grams anhydrous sodium sulfate wereadded to the solution and a solution of 8.8 grams of acetaldehyde in 50milliliters of absolute methanol was then added dropwise with stirringover a period of approximately 10 minutes, to keep the temperature ofthe reaction mixture under forty degrees centigrade. The hot mixture wasstirred for about two hours at room temperature. The drying agent wasfiltered of) and the solvent removed under vacuum.

The crude product obtained in a ninety percent yield was an almostcolorless, odorless oil. Phosphorus found, 15.0 percent. (Calculated forC l-l O NP): 15.7 percent.

b. Preparation and Characterization of the picrate ofdimethyl-N-(2'hydroxyethyl)-2-aminoethyl-Z-phosphonate.

1 2/10 grams of the crude oily dimethyl-N-(2'-hydroxyethyl)-2-aminoethyl-Z-phosphonate was completely dissolved in a mixture of 50parts of ether and 25 parts of methanol by volume. A solution of 3.5grams of picric acid in a mixture of three hundred cc. of ether andtwenty cc. of methanol was then added.

The turbid solution was filtered and the filtrate evaporated to drynessat twenty-five degrees ccntigrade under sixteen millimeters Hg. Thecrude picrate was recrystallized twice from hot ethyl-acetate by coolingat minus twenty degrees centigl'ade.

The yellow crystalline product sinters at 109 C, and melts at 1 l 1.5 tol 12.5 (uncorrected) with decomposition.

ANALYSIS PERCENT Formula: CIQHIBOIXNIP Calculated Found c 33.81 33-80 H4.49 459 N 13.14 1317 P 7.26

7.18 (flame spectroscopy) EXAMPLE 3 Using the same general procedure asin the foregoing examples, 15.6 grams of acetone was added portionwisewith stirring into a solution of 22.0 grams of dimethyl hydrogenphosphite and 21.02 grams diethanolamine dissolved in milliliters ofmethanol and containing fifty grams of anhydrous sodium sulfate. Thetemperature rose to 30 C. during the addition.

The reaction mixture was refluxed for 5 minutes and, after cooling andfiltering off the drying agent, the solvent was removed as in Example 1.

The crude product is a very viscous, almost colorless liquid. Phosphorusfound: 12.9 percent (Calculated for C H NP 12.13 percent). The compoundis named dimethyl-N,N-bis( 2- hydroxy-ethyl)-2-aminoisopropyl-2-phosphonate.

EXAMPLE 4 Twenty-two grams of dimethyl phosphite was dissolved in 150milliliters methanol. To the mixture was added 50 grams anhydrous sodiumsulfate and a solution of 11.6 grams of acetone and 25 milliliters ofmethanol. Thereafter, 12.2 grams of ethanolamine dissolved in 20milliliters methanol was added dropwise over a period of 4 minutes,during which time the temperature rose to 41 C. The reaction mixture wasstirred for several hours and allowed to stand. The sodium sulfate wasremoved by suction filtration and the solvent evaporated to provide a 95percent yield of crude product.

EXAMPLE 5 To a mixture of 234.2 grams of diphenyl phosphite and onehundred milliliters methanol was added 61.1 grams of ethanolamine. Thetemperature rose to 1 12 C, after which an additional 150 milliliters ofmethanol were added. The reaction mixture was agitated for nearly 2hours. To a mixture of two hundred and 47 grams of the resultingsolution and 31.5 grams of anhydrous sodium sulfate was added dropwisewith agitation over a 6 minute period, a solution of 36.3 grams ofacetone and 25 milliliters of methanol. The reaction was allowed to stirfor minutes.

EXAMPLE 6 To a mixture of 234.2 grams of diphenylphosphite and 150milliliters of methanol was added a solution of 72.6 grams of acetone in50 milliliters of methanol. An additional 50 milliliters of methanolwere added to the reaction mixture and after 10 minutes, 63 gramsanhydrous sodium sulfate was added. Thereafter 61.1 grams ethanolaminewere added dropwise with agitation over a period of 12 minutes. Afterstanding at room temperature for a period of time, the volatiles wereevaporated and the crude product weighed 378 grams.

The polyfunctional monomers of this invention readily react withpolycarboxylic compounds to form polyesters. The preferred carboxyliccompounds are'the carboxylic acids, acid halides and acid anhydrides,and mixtures thereof. The carboxylic compounds can be saturated orunsaturated or mixtures thereof depending upon the intended use for thepolyesters. Likewise the polyc rboxylic compounds can be aliphatic,cycloaliphatic, aromatic or heterocyclic. Illustrative polycarboxyliccompounds include the following: phthalic acid, isophthalic acid,terephthalic acid; tetrachlorophthalic acid; maleic acid, dodecylmaleicacid; octadecenylmaleic acid; fumaric acid; aconitic acid; itaconicacid; trimellitic acid; tricarballylic acid; 3,3-thiodipropionic acid;4,4'-sulfonyl dihexanoic acid; 3-0ctenedioic-l,7-acid; 3-methyl3-decenedioic acid; succinic acid; adipic acid;1,4-cyclohexadiene-l,2-dicarboxylic acid; 3-methyl-3,S-cyclohexadienel,Z-dicarboxylic acid; 3-chloro-3 ,S-cyclohexadiene- 1 ,Z-dicarboxylicacid; 8,12-eicosadienedioic acid; 8-vinyl-l0-octadecenedioic acid; andthe corresponding acid anhydrides, acid chlorides and acid esters, suchas phthalic anhydride, phthaloyl chloride, and the dimethyl ester ofphthalic acid. The resins can be modified for special properties byusing other selected polycarboxylic compounds. For example,l,4,5,6,7,7-hexachlorobicyclo-(2.2. l )-5-heptene-2,3 -dicarboxylicanhydride or acid and tetrachlorophthalic anhydride or acid can be usedto impart additional flame resistance to the composition. The monomersof this invention can also be reacted with monobasic acids, such asacetic acid, propionic acid, butyric acid and the like, to produceesters that are useful as plasticizers.

The esterification or etherification of the phosphorus-containingmonomers of this invention can be carried out at elevated temperatures,preferably not over one hundred and fifty degrees centigrade. Whenpolycarboxylic acids are used, the progress of the esterificationreaction can be monitored by measuring the quantity of water ofesterification that is produced. Small quantities of toluene or xylenecan be used as azeotroping agents to facilitate removal of the water.When acid halides are used, it is preferred to use solvents during thereaction. The acid halide can be dissolved in a suitable solvent such asbenzene and methylene dichloride and added to the hydroxyetherderivative also dissolved in the same or a similar solvent. The reactioncan be conducted at a temperature up to the boiling point of thesolvent. The solvent can be readily removed such as by stripping at thecompletion of the reaction. The progress of the reactions involving theacid halides can be monitored by measuring the quantity of hydrogenhalide evolved during the course of the esterification. Moreover, in thereactions involving the acid halides, it is often advantageous to use ahydrogen halide acceptor such as amines and strong bases. Preferredacceptors are tertiary amines such as pyridines, and triethylarnine.

The unsaturated polyesters produced in accordance with this inventioncan be cured by crosslinking in the presence of a catalytic amount of aconventional polymerization catalyst for addition polymerization ofethylenically unsaturated materials, including free radical catalystssuch as benzoyl peroxide and other organic peroxides. The polymer canalso be cured by copolymerization with an ethylenically unsaturatedmonomeric material copolymerizable therewith, and preferably in thepresence of a catalytic amount of a polymerization catalyst such asmentioned above.

The ethylenically unsaturated monomers which can be used in curing orcross-linking the ethylenically unsaturated polymers of the presentinvention can be varied widely. While other materials can be used, it ispreferred that addition polymerization be practiced since no by-productammonia, water, etc., is formed and the problems resulting therefrom arenot experienced. The monomers useful in curing the thermoplasticunsaturated polymers include vinylidene compounds or mixtures thereofcapable of cross-linking ethylenically unsaturated polymer chains attheir points of unsaturation and usually they contain the reactive groupH C C. Specific examples include styrene, chlorostyrenes, methylstyrenes such as alpha methyl styrene, p-methyl styrene, divinylbenzene, indene, unsaturated esters such as: methyl methacrylate, methylacrylate, allyl acetate, diallyl phthalate, diallyl succinate, diallyladipate, diallyl sebacate, diethylene glycol bis(allyl carbonate),triallyl phosphate and other allyl esters, and vinyl toluene, diallylchlorendate, diallyl tetrachlorophthalate, the lower aliphatic estersother than methyl of methacrylic and acrylic acids, the diacrylate,dimethacrylate, diethacrylate esters of ethylene glycol, etc. Themonomer can be admixed in the polymer in an amount sufficient to producea thermoset polymer and the admixture heated to an elevated temperaturein the presence of a suitable catalyst to cross-link or cure thepolymer. With proper catalyst systems such as cobalt naphthenate andmethylethyl ketone peroxide, room temperature cures are obtained.

In accordance with still other aspects of the invention, it is possibleto employ the improved polymers of the invention in the preparation ofplastic articles in general, reinforced plastic articles containing areinforcement such as cloth, glass fibers in the form of rovingindividual glass fibers, etc., and laminates or other filled resincompositions. Surprisingly, such prepared materials exhibit vastlyimproved physical properties such as discussed above for the polymers ofthe invention. Suitable reinforcements or laminations for preparing thereinforced articles and laminates include textile fibers or cloth, glassfibers or cloth, roving, etc. Casting may be prepared from the improvedpolymers of the present invention and such products likewise have beenfound to exhibit the improved properties of the polymers discussed aboveto a surprising degree. In

It) I043 U249 general, well known processes of the prior art may be usedfor preparing the above-mentioned plastic articles, reinforced plasticarticles, laminates or other filled resin compositions, and castings,with the exception of substituting the improved polymer of the inventionfor that conventionally used. Usually, other changes in the process arenot necessary. It is usually preferred that a thermoset polymer bepresent in the finished article.

The following are examples of suitable reinforcing media that can beused with the polymers of the invention: glass fibers, glass mats, glasscloth, synthetic fibers such as orlon, mineral fibers such as asbestos,natural fibers such as cotton silk and wool, and metallic fibers such asaluminum and steel.

Following are examples of fillers that can be used in the polymers ofthe invention: inorganic materials such as calcium carbonate, clay andpigments, and organic materials such as wood flour, cotton and rayonflock, sisal fibers and dyes.

It is also within the scope of the invention to bend thephosphorus-containing monomers and the polyesters and polyetherscontaining the phosphorus-containing compounds of this invention andother hydroxyl-containing materials, such as polyesters. Such additionalpolyesters are the reaction products of polycarboxylic acids andpolyhydric alcohols, The polycarboxylic compounds which can be employedare any of the polycarboxylic compounds disclosed hereinbefore. Thepreferred polycarboxylic compounds are the aliphatic and cycloaliphaticdicarboxylic acids containing no more than 14 carbon atoms, and thearomatic dicarboxylic acids containing no more than 14 carbon atoms.Polyphenolic compounds which can be employed are the reaction productsof phenolic compounds with aldehydes, such as phenol-formaldehyderesins. Illustrative polyhydric alcohols include the following;glycerol; polyglycerol; pentaerythritol; mannitol; trimethylol propane;sorbitol; trimethylolethane; butanediol; pentanediol; 1,2,6-hexanetriol;2,2,-bis(4-hydroxyphenyl)-propane, and the like. Preferred polyols arethe open-chain aliphatic polhydric alcohols and polyalkylene etherpolyols possessing from two to six esterifiable hydroxyl groups andcontaining no more than 20 carbon atoms.

The following example illustrates the preparation of a novel polymericcomposition of a phosphorus-containing compound of this invention.

EXAMPLE 7 A phosphorus-containing polyester was prepared as follows:

A polyester was prepared by reacting ten moles of trimethylolpropane andsix moles of adipic acid; the resulting hydroxyl number was five hundredand four. To 500 grams of this polyester was mixed 125 grams ofdimethyl-N-(2'-hydroxyethyl)-2-amino-isopropyl-2-phosphonate. Themixture, which was non-homogeneous, was heated and stirred at 1 10 C.for 4.5 hours under vacuum. Methanol vapor was condensed and recoveredfrom the reaction mixture. The resulting product was clear and had aphosphorus content of about 3.1 percent and a Gardner viscosity of 240seconds at 50 C.

In instances wherein the phosphorus-containing compounds of thisinvention are utilized with the hydroxyl-containing polymeric materialssuch as the polyesters disclosed herein, it

is preferred that said hydroxyl-containing polymeric material have ahydroxyl number between 30 and 950.

As shown in the foregoing Example 7, the phosphorus-containing compoundsof this invention can be reacted with polyesters, that are the reactionproducts of polycarboxylic compounds and polyhydric alcohols of the typedisclosed hereinbefore, to produce phosphorus-containing polyesters.Hence, it is apparent that while this invention has been described withreference to certain specific embodiments, many variations will berecognized by those skilled in the art that do not depart from thespirit and scope of the invention.

What is claimed is:

l. A polyester produced by the process comprising the reacting at atemperature not over C:

l. a compound having the formula:

wherein m and n are zero to 2 and m+n equals 2; a is zero to l, b is lto 2 and a+b equals 2; X is oxygen or sulfur; R and R, are alkyl of oneto eight carbon atoms, cycloalkyl of three 0 eight carbon atoms, alkenylof three to four carbon atoms, aryl ofsix to eight carbon atoms,alkylaryl of seven to eight carbon atoms, arylalkyl of seven to eightcarbon atoms or halo-substituted organic radicals of the foregoing groupwherein the halogen is chlorine or bromine, R and R are hydrogen, alkylof one to eight carbon atoms, cycloalkyl of three to eight carbon atoms,alkenyl of three to four carbon atoms, aryl of six to eight carbonatoms, alkylaryl of seven to eight carbon atoms, or arylalkyl of sevento eight carbon atoms; and R is an alkylene group of one to eight carbonatoms with 11. an hydroxyl terminated polyester which is the reactionproduct of A. a polycarboxylic compound selected from the groupconsisting of diand tricarboxylic acids, diand tricarboxylic acidhalides, diand tricarboxylic acid anhydrides and mixtures thereof and B.a polyol selected from the group consisting of open chain aliphaticpolyhydric alcohols and polyalkylene ether polyols possessing from 2-6esterifiable hydroxyl groups and containing up to 20 carbon atoms. 2.The polyester of claim 1 wherein the phosphorus compound has theformula:

3. The polyester of claim 2 wherein the phosphorus compound isdimethyl-N-(2'-hydroxyethyl)-2-aminoisopropyl-2- phosphonate.

4. The polyester of claim 3 wherein the polycarboxylic compound isadipic acid and the polyhydric alcohol is trimethylolpropane.

2. The polyester of claim 1 wherein the phosphorus compound has the formula:
 3. The polyester of claim 2 wherein the phosphorus compound is dimethyl-N-(2''-hydroxyethyl)-2-aminoisopropyl-2-phosphonate.
 4. The polyester of claim 3 wherein the polycarboxylic compound is adipic acid and the polyhydric alcohol is trimethylolpropane.
 11. an hydroxyl terminated polyester which is the reaction product of A. a polycarboxylic compound selected from the group consisting of di- and tricarboxylic acids, di- and tricarboxylic acid halides, di- and tricarboxylic acid anhydrides and mixtures thereof and B. a polyol selected from the group consisting of open chain aliphatic polyhydric alcohols and polyalkylene ether polyols possessing from 2-6 esterifiable hydroxyl groups and containing up to 20 carbon atoms. 